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145 Cards in this Set
- Front
- Back
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azido-
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RN3
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diazo
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RN2+
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determination of enantiomeric rotation
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cannot be determined by structure, only experiment
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stereoisomers
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differ only by how atoms are oriented in space
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E/Z
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Z is when highest priority on same side
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R/S
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R is CW, S is CCW
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diastereoisomers
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stereoisomers that are not mirror images
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possible stereoisomers
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with n stereocenters, 2^n
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meso compound
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molecule with 2 or more chiral centers with a plane of symmetry (no optical activity)
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torsional strain
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when cyclic molecules must assume conformations with eclipsed interactions
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nonbonded strain
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sterric hindrance when atoms/groups compete for the same space
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nucleophilicity of nucleopiles with same attacking atom
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increases with basicity with same attacking atom
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nucleophilicity in protic solvents
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doesn't correlate to basicity, instead usually large nucleophiles that can shed solvent are better (I-,HS-,RS- > Br-, HO-, RO-, CN-, N3- > NH3, Cl-, F-, RCO2- > H2O, ROH > RCO2H
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nucleophilicity in aprotic solvents
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because nucleophiles are naked so basicity is again defines strength of nucleophile (F- > Cl- > Br- > I-)
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leaving group ability
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best groups are weak bases (can accept electron pair) (I- > Br- > Cl- > F-) (best groups are TsO-, H2O, NH3, worst groups are OH-, NH2-, RO-)
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SN1 conditions
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stabilized intermediate by polar/protic solvent, needs good leaving group, favored by bulky nucleophiles at more substituted carbons
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SN2 conditions
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strong nucleophile, less substituted carbons, best in apolar solvents, less bulky nucleophiles work
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degrees of unsaturation
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N=(1/2)(2n+2-m)
N is number of double bonds or rings formula: CnHm |
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E1 conditions
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highly polar solvent, branched carbon chains, good leaving group, weak and low concentration of nucleophiles, favored over SN1 by higher temperatures (hard to control, though)
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E2 conditions
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sterric hindrance is less of an issue for E2 than SN2 (no backside attack), strong base favors E2 and weak lewis base/good nucleophile favors SN2
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anti-Markovnikov halide addition to alkene
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radical addition of halogen (Br plus hv)
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1,2 diol from alkene
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cold, dilute potassium permanganate
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oxidation of alkenes (carboxyllic acids and ketones)
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Add potassium permangante, hydroxide, heat followed by acidic workup (break through double bond form carboxyllic acid for singly substituted and ketone for double substituted, CO2 for terminal)
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ozonolysis
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alkene can be turned into aldehyde by ozone in dichloromethane followed by zinc and water (alcohol formation is sodium borohydride and methanol)
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alkene to epoxide
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peroxycarboxylic acids (m-chloroperoxybenzoic acid)
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polymerization of alkene
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radical carbon, heat high pressure (radical mechanism, sometimes anionic or cationic)
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n-butyl lithium
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acts as base to form acetylide ion which can nucleophilically attack an alkyl halide to add that R group
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alkyne to cis alkene
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H2, Pd, barium sulfate and quinoline
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alkyne to trans alkene
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sodium, liquid ammonia
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hydroboration of alkynes
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internal: add BH3 to form BR3 (R=alkene), then acetic acid to form three enols (tautomerize to ketone)
terminal: must start with BR2H with H2O2 and hydroxide (aldehyde/enol) |
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alkyne oxidation to acids
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internal: potassium permanganate/hydroxide followed by acidic workup
terminal: ozone in carbon tetrachloride followed by water workup |
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aromatic halogenation
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Br: Br2/FeBr3, Cl: Cl2/FeCl3 (AlCl3), F: multisubstituted, I: not reactive
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aromatic sulfonation
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sulfur trioxide and sulfuric acid with heat (adds SO3H)
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aromatic nitration
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nitric acid and sulfuric acid (passes through nitronium ion electrophilic intermediate, which loses proton)
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Friedel-Crafts acylation
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carbocation electrophile (acyl chloride) is incorporated with AlCl3 to add carbonyl onto ring
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activating and ortho/para
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NH2, NR2, OH, NHCOR, OR, OCOR, R (all electron-donating)
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deactivating and ortho/para
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halogens (weakly electron withdrawing)
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deactivating and meta
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NO2, SO3H, carbonyls (COOH, COOR, COR, CHO) (electron withdrawing)
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aromatic reduction
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H2, Rh/C at high temperature and pressure
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acid/ester reduction
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LAH, acid (acid to alcohol, ester to ether)
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ketone/aldehyde reduction
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sodium borohydride and acid (both form alcohols)
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aniline to phenol
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nitrous acid/sulfuric acid to form diazonium salt, addition of acid displaces to form phenol
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alcohol to alkene
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sulfuric acid and heat, hydride shift can occur to form more substituted double bond
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conversion of OH leaving group
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acid to form water, tosyl chloride to form tosylate
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alcohol to alkyl halide
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SOCl2 to form inorganic ester which is displaced by chloride to form alkyl halide (PBr3 for bromide)
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PCC reagent
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converts primary alcohol to aldehyde
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secondary alcohol to ketone
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sodium dichromate, sulfuric acid OR CrO3 and sulfuric acid in acetone
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primary alcohol to acid
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sodium dichromate and sulfuric acid OR CrO3 and sulfuric acid in acetone OR potassium permanganate
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phenol to quinone
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sodium dichromate and sulfuric acid
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Michael addition
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form enolate carbanion by strong base (LDA, KH) by anstraction of proton between two carbonyls, adds to beta carbon of alpha,beta-unsaturated carbonyl compound
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hydrate formation
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addition of water to carbonyl
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acetal formation
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addition of alcohol to aldehyde
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ketal formation
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addition of alcohol to ketone
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cyanohydrin formation
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addition of cyanide to carbonyl (OH and CN on same carbon)
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imine formation
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addition of ammonia to carbonyl (reactive pair of lone pair electrons on nitrogen after addition)
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aldol condensation
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in base, enolate from one carbonyl adds to another carbonyl (acid, enol) to form beta-hydroxy ketone (heat and base allows for elimination to alpha,beta-unsaturated carbonyl)
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Wittig reaction
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formation of ylide after reacting (C6H5)3P with alkyl halide (phosphonium salt), ylide attacks carbonyl, cyclic mechanism forms C-C double bond (strong P=O bond formed drives reaction)
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oxidation of carbonyls to acids
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potassium permanganate, CrO3, silver oxide, hydrogen peroxide
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reduction of carbonyl to alcohol
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LAH or sodium borohydride
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Wolff-Kishner reduction
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carbonyl is converted to hydrazone, releases N2 when heated in base to alkane (mercury and zinc in HCl works for compounds unstable in base)
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ester from acid
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under acidic conditions, addition of alcohol and release of water as carbonyl group reforms
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formation of acid chloride
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add SOCl2, PCl3, or PCl5 (for bromide add PBr3)
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beta-keto acid decarboxylation
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ketone oxygen grabs acid proton, which adds to C=O acid group and sigma bond connecting acid to alpha carbon breaks to form enol (ketone) and CO2
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acid halide reactions
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hydrolysis to carboxylic acid, conversion to ester and HCl by alcohol addition, amide formation in excess ammonia (2 equiv.), F-C acylation, reduction by H2/Pd/BaSO4 to aldehyde
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anhydride synthesis
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acid chloride plus carboxylic salt or form cyclic anhydride to a 5 or 6 membered ring
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anhydride reactions
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hydrolysis to 2 acids, ammonia cleavage to amide and acid, ester conversion by alcohol, F-C acylation with AlCl3 to add acid part to ring
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formation of amides
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react acid chloride with amine (not teritary, no hydrogens to lose)
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amide to amine
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LAH reduction (no carbon atom is lost, as in Hoffmann rearrangement)
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Hoffmann rearrangement
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addition of BrO- to amide, Br adds to nitrogen, proton is removed from nitrogen to form a negatively charged nitrogen, R group attacks nitrogen while lone pairs attack CO carbon and Br acts as leaving group (nitrene is negatively charged nitrogen, isocynate is back-to-back O,C,N double bonds with N bound to R
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ester reactions
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hydrolysis (saponification) by acid or base, conversion to amide (NH3 displaces), transesterification (exhange of alcohols), Grignard addition (forms tertiary alcohol through ketone intermediate), Claisen condensation to beta-keto ester, hydrolysis by LAH to 2 alcohols (CO and OR bond split)
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Claisen condensation
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enolate ester adds to another ester to form beta-keto ester and an alcohol leaving group
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reactivity of acid derivatives
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acyl halides > anhydrides > esters > amides
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amine synthesis
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react alkyl halide with ammonia, to prevent extra reactions with alkyl halides NH3 should be joined with o-phthalic acid to form phthalimide (good nucleophile when deprotonated) to react with alkyl halide followed by NaOH to remove phthalic acid group
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nitro compound to aniline compound
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addition of zinc and dilute HCl
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nitrile to amine
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LAH reduction
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carbonyl to amine
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add amine to form imine, then H2 and Nickle (Raney Nickle) to reduce to amine (amine formed has one greater carbon connectivity than starting amine)
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amine to alkene
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excess MeI to form quaternary ammonium iodide salt, Ag2O/H2O forms ammonium hydroxide salt, heat displaces nitrogen group to form less substituted alkene
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carbon tetrachloride
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nonpolar, inert solvent
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chloroform
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polar, nonflammable solvent
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dochloromethane
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polar, nonflammable solvent
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DIBAL (diisobutylaluminum hydride)
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selective reduction of esters, amides, and nitriles to aldehydes
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dicyclohexylborane
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hydroboration of alkyne derivatives (anti-Markovnikov hydration)
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dioxane
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good solvent for dissolving water and organic substrates
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DMD (dimethyldioxirane)
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epoxidation of alkenes
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DMF (dimethylforamide)
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polar aprotic solvent
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DMSO (dimethylsulfoxide)
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polar aprotic solvent
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Et2O (diethyl ether)
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medium polarity solvent
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Hg(OAc)2 (mercuric acetate)
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oxymercuration (hydration of alcohol without unwanted rearrangements on carbocation formation), sodium borohydride is second step
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HgSO4 (mercuris sulfate)
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Markovnikov of alkynes
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metaperiodic acid (HIO4)
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oxidative cleavage of 1,2-diols
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LDA (lithium diisopropylamine)
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strong, hindered base
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Lindlar's catalyst
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Pd/CaCO3/Pb(OAc)2/quinoline; reduces alkynes to cis-alkenes
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mCPBA (m-chloroperbenzoic acid)
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epoxidation of alkenes
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sodium nitrite (NaNO2)
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diazotization of amines (with HCl)
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NBS (N-bromosuccinimide)
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adds bromine at allylic site
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NCS (N-chlorosuccinimide)
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adds chlorine at allylic site
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Osmium tetroxide (OsO4)
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Dihydroxylation of alkenes (1,2-diols)
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triphenylphosphine (PPh3)
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making wittig reagents
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tetrahydrofuran (THF)
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medium polarity solvent
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Zn(Hg) (zinc amalgam)
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Clemmensen reduction with HCl
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extraction
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transfer dissolved compound from one solvent into another in which it is more soluble so impurities left in first solvent
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gravitation filtration
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isolation of product in filtrate and leave impurities in solid (hot solvent)
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vacuum filtration
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isolation of solid product from filtrate
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recrystalization
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impure crystals dissolved in minimum amount of hot solvent and as it is cooled, the crystals reform and leave impurities behind
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mixed solvent system of recrystalization
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crude compound dissolves in solvent where it is highly soluble, add another solvent in which compound is less soluble in drops until crystals appear, heat solution and cool slowly for crystals
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sublimation
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heated solid turns directly to gas at low pressure and elevated temperature (cooled on cold finger), leaves impurities behind as they don't sublime
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simple distillation
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separate liquids that boil below 150 C and at least 25 C apart
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vacuum distillation
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boil above 150 C and at least 25 C apart (low pressure to prevent decomposition)
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fractional distillation
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separate liquids that boil less than 25 C apart (vaporation then condensation up a tube so material becomes more and more separated)
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TLC
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nonpolar compounds migrate the fasted (highest Rf values), solid phase is polar for silica gel, viewing spots by UV or iodine staining
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electrophoresis migration velocity
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v = (Ez/f)
E is electric field strength, z is net charge of molecule, f is frictional coefficient (depends on mass/shape) |
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IR
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molecular vibrations (stretching, bending, rotating), fingerprint region is 1500-400 1/cm
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IR peaks (alkanes, alkenes, alkynes, aromatic, alcohols)
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alkane: 2800-3000 (C-H), 1200 (C-C)
alkene: 3080-3140 (=C-H), 1645 (C=C) alkyne: 2200 (C,C), 3300 (C,H) aromatic: 2900-3100 (C-H), 1475-1625 (C-C) alcohols: 3100-3500 (broad) |
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IR peaks (ethers, aldehydes, ketones, acids, amines)
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ether: 1050-1150 (C-O)
aldehyde: 2700-2900 ((O)C-H), 1725-1750 (C=O) ketone: 1700-1750 (C=O) acid: 1700-1750 (C=O), 2900-3300 (O-H) amine: 3100-3500 (sharp) |
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NMR chemical shifts
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CH3, CH2, CH, alyllyic hydrogens (.8-2.3); ketone alpha hydrogens, benzylic hydrogens, alkyne terminal hydrogens, alpha amine hydrogens (connected to carbon connected to nitrogen) (2-3); CH connected to I, Br, Cl, F, O (2.8-4.7); terminal alkene, internal alkene (4.5-5.5); aromatic hydrogens (7-7.5); aldehyde hydrogens (9-10); acid hydrogens (10-13)
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coupling constant and Karplus curve
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coupling constant is space between individual peaks of a pattern (same for two sets of hydrogens acting on each other), Karplus curve shows that the coupling constant is maximized when protons are anti and high when they are syn but lowest when angle between is 90 degrees
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coupling constant and aliphatics
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vicinal is a good amount lower than geminal
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coupling constant and olefinic
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maximum in trans on neighboring carbons, medium in cis on neighboring carbons (there is a small coupling between protons on the same carbon)
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multiple couplings
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make tree diagram with first coupling and couple this based on next sets of similar protons
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sugar stereochemistry
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losest OH on left is L and right is D
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epimers
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diastereoisomers that differ at one carbon
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sugar straight chain to ring
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any group on right in Fischer projection points down and groups on left point up, carbonyl carbon becomes chiral
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anomers
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beta is when C1 OH and CH2OH are in cis and alpha is when they are in trans, alpha is less favored because OH is made axial
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Benedicts solution
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Cu(OH)2, oxidizes reducing sugars that have OH on their C1 carbon
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specific rotation
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specific rotation=observed rotation divided by concentration (g/mL) times length (dm) (depends on number of molecules that are encountered)
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alkane properties
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higher moleculer weight means higher MP/BP/density, branching reduces MP/BO (fewer van der waal forces as liquid and less packing ability as solid)
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alkane nomenclature
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1. find longest chain
2. number chain so substiuents get lower numbers 3. name substituents (use di, tri if more than one of same group) 4. assign each substituent at number 5. list substituents in alphabetical order (ignore di,tri..., tert, sec, or n but NOT cyclo, iso, neo) |
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sec and iso butyl
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sec is when methyl is on carbon connected to main chain and iso is when it is one further away
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alkene properties
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Higher MW means higher MP/BP, terminal alkenes have lower BP, trans alkenes have higher MPs (better packing) and cis alkenes have higher BPs (polarity)
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alkyne properties
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BPs are slightly higher than corresponding alkenes, internal alkynes have higher BPs than terminal, larger dipole moments than alkenes, terminal alkynes are relatively acidic
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alcohol properties
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higher BPs than hydrocarbons and ketones/aldehydes (lower than acids), weakly acidic (phenol more acidic, slightly soluble in water), H-bonding
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ether properties
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no H-bonding, low BPs, only slightly polar/soluble in water, mostly inert
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ether cleavage
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high temperature and acid, ether oxygen is protonated and nucleophile adds to less hindered R in SN2 (in SNI less hindered side leaves to form bulkier carbocation)
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aldehyde/ketone properties
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dipole moments cause elevation in BP but not as much as alcohols
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carboxylic acid properties
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can form H-bonded dimers, resonance of anion, stability of salt increased by electron withdrawing groups (dicarboxylic acid), alpha hydrogens are acidic
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amine properties
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BPs are greater than alkanes and less than alcohols (not as great H-bonding and none in tertiary amines), sp3 hybridization (flipping around lone pair), alkyl amines are even more basic as alkyl groups can stabilize the charge, aniline is less basic (electron density removed)
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ultraviolet spectrum electron transitions
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π->π* transitions are easier than n->π* transitions even though the second involve lower energy difference (HOMO->LUMO transitions)
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pinacol rearrangement
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1,2-diol becomes a ketone in acid through a cationic intermediate following a OH2 leaving group and an R group migrates
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protection of alcohols
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protection from basic conditions involves the addition of dihydropyran to form a tetrahydropyranol ether, acid can remove protecting group
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acetoacetic ester synthesis
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ester plus any carbonyl in base to form alcohol leaving group after addition (acidic workup)
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Cope rearrangement
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1,5-dienes
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carboxylic acid preparation
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alkyl halide (RX) plus Magnesium in THF solvent, then bubble CO2 through to make RCOOH
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epimers and anomers
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an anomer is a specific type of epimer that has reversed position at the C-1 carbon of sugars (epimers are those that are stereoisomers with differences at 1 of any carbons)
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terpenes
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derived from isoprene units (C5H8)n
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steroids
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terpenoid lipid with 4 rings
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